CN104640952B

CN104640952B - Contact adhesive composition

Info

Publication number: CN104640952B
Application number: CN201480002449.XA
Authority: CN
Inventors: 金基映; 金鲁马; 黄仁浩; 朴寅圭
Original assignee: LG Chemical Co Ltd
Current assignee: LG Corp
Priority date: 2013-06-19
Filing date: 2014-06-19
Publication date: 2016-08-17
Anticipated expiration: 2034-06-19
Also published as: US20150093533A1; WO2014204249A1; TW201512358A; TWI586782B; JP2015536354A; TWI568818B; TW201516106A; EP2886623B1; EP2891693B1; CN104640952A; CN104640951A; WO2014204250A1; JP5999270B2; JP6132219B2; JP2016502578A; EP2891693A1; EP2886622A4; US20150368520A1; US20150099114A1; US9868883B2

Abstract

The application relates to adhesive composition, protecting film, optical element and display device.Adhesive composition according to the application has the storage stability of excellence, and after forming cross-linked structure, shows suitable low speed and high speed peel strength, and have the excellent balance between two kinds of peel strengths.Therefore; when described adhesive composition is put on such as protecting film, show the protected effect of excellence, and be easily stripped when to peel off at a high speed; thus the present invention is applicable to High-speed machining field, and during High-speed machining, show the antistatic behaviour of excellence.

Description

Contact adhesive composition

Technical field

The present invention relates to contact adhesive composition, for protecting the film of optics, optics and display device.

Background technology

Protecting film may be used for preventing the dirt on optics such as Polarizer, multiple plastic product, electronic product or automobile The adhesion of dye thing such as dust and scratch.Protecting film can need suitable peel strength and antistatic property.

Such as, when peeling off protecting film in order to use the other products of product or assembling with high speed, need relatively low Peel strength (hereinafter referred to as " high speed peel strength ").But, when peeling off protecting film with low speed, protecting film can be relatively High peel strength (hereinafter referred to as " low-rate release strength ") shows suitable defencive function.

Additionally, the electrostatic produced by the stripping of protecting film can cause pouring in of pollutant such as dust, if electronics produces Product, can cause electrostatic breakdown or the device fault of device.Especially, recently due to the use of computer and liquid crystal TV or movement The multifunction of phone, assembly is integrated, so the problem that electrostatic causes is on the rise.

Thus, attempt the contact adhesive for comprising in protecting film and anti-static function is provided.

Such as, in patent documentation 1, attempt by ethylene-oxide-modified dioctyl phthalate plasticizer is added Contact adhesive suppresses the generation of electrostatic.Additionally, in patent documentation 2, make organic salt mix with contact adhesive；And In patent documentation 3, slaine and chelating agen is made to mix with contact adhesive.But, according to said method, it may occur that by pressing Sensitive adhesive component is transferred to the pollution that product to be protected is caused, it is difficult to the electrostatic that suppression produces in early days, and for obtaining Low-rate release strength important for defencive function reduces too much.

[prior art literature]

[patent documentation]

(patent documentation 1) Japanese Patent Patent application No.1993-140519

(patent documentation 2) Korean unexamined patent publication no No.2004-0030919

(patent documentation 3) Korean unexamined patent publication no No.2006-0128659

Summary of the invention

Goal of the invention

The application provides contact adhesive composition, for protecting the thin film of optics, optics and display device.

Solution

Exemplary pressure-sensitive compositions can comprise polymer, ionic compound and cross-linking agent.In contact adhesive group In compound, polymer can be the polymer with crosslinking points, and can react to form cross-linked structure with cross-linking agent.

Polymer can comprise, and such as, polymerized unit and the conduct of the monomer comprising alkylidene oxide chain have nitrogen-atoms The polymerized unit of dialkyl group (methyl) acrylamide of monomer.Here, dialkyl group (methyl) acrylamide can comprise have 1 to 20, the alkyl of 1 to 16,1 to 12,1 to 8 or 1 to 4 carbon atom.Terms used herein " monomer " refers to can be anti-by polymerization The all types compound of polymer should be formed, and term " polymerized unit of monomer " represents such a state: monomer is It is polymerized and is contained in the side chain of polymer or the skeleton of main chain.

The compound represented by formula 1 can be used as the monomer with alkylidene oxide chain:

[formula 1]

In formula 1, Q is hydrogen or alkyl, and U is alkylidene, and Z is hydrogen, alkyl or aryl, and m is Arbitrary Digit, such as, and 1 to 12 Number.

In formula 1, when there is at least two [-U-O-] unit, the carbon number of the U in each unit can be identical or not With.

In formula 1, m can be, such as, and the number of 1 to 16,1 to 12 or 1 to 10.When within the above range, in the system of polymer The degree of crystallinity of standby middle polymerization efficiency and polymer is positively retained in proper range, and can provide suitably conduction to contact adhesive Property.

Unless otherwise specifically limited, term used herein " alkyl " can be have 1 to 20 carbon atom, 1 to 16 Carbon atom, 1 to 12 carbon atom, 1 to 8 carbon atom or the alkyl of 1 to 4 carbon atom.Alkyl can be straight chain, branched or Ring-type.Alkyl can be unsubstituted, or is replaced by least one substituent group.

Unless otherwise specifically limited, term used herein " alkylidene or alkylene base (alkylene or Alkylidene group) " can be that there is 1 to 20 carbon atom, 1 to 16 carbon atom, 1 to 12 carbon atom, 1 to 8 carbon Atom or the alkylidene of 1 to 4 carbon atom or alkylene base.Alkylidene or alkylene base can be straight chains, branched or ring-type 's.When needed, alkylidene or alkylene base can be replaced by least one substituent group.

In another embodiment, in formula 1, Q can be alkyl, such as, have 1 to 8 carbon atom or 1 to 4 carbon The alkyl of atom.When the compound using wherein Q to be alkyl, such as, contact adhesive composition is applied in protecting film, can Advantageously protecting film can be removed easily and not have residue or spot on adherend.

Unless otherwise specifically limited, term used herein " aryl " can be derived from comprise wherein contain phenyl ring, The knot that at least two phenyl ring is connected or at least two phenyl ring shares one or at least two carbon atom is fused to each other or is bonded The monovalence residue of the compound or derivatives thereof of structure.Aryl it may be that such as, has 6 to 25 carbon atoms, 6 to 22 carbon former Son, 6 to 16 carbon atoms or the aryl of 6 to 13 carbon atoms.Aryl can be phenyl, phenethyl, phenylpropyl, benzyl, toluene Base, xylyl and naphthyl.

In this manual, specific functional group, such as may replace the substituent group on alkyl, alkylene base or alkylidene, Can be but be not limited to: alkyl, alkoxyl, thiazolinyl, epoxy radicals, cyano group, carboxyl, acryloyl group, methylacryloyl, acryloyl-oxy Base, methacryloxy or aryl.

The compound of formula 1 can be but be not limited to: (methyl) alkyl acrylate epoxide two alkylene diol ester, (methyl) alkyl acrylate Epoxide three alkylene glycol ester, (methyl) alkyl acrylate epoxide four alkylene glycol ester, (methyl) acrylic acid aryloxy group two alkylene glycol One in ester, (methyl) acrylic acid aryloxy group three alkylene glycol ester and (methyl) acrylic acid aryloxy group four alkylene glycol ester or At least two.

Here, alkoxyl can be, such as, have 1 to 20 carbon atom, 1 to 16 carbon atom, 1 to 12 carbon atom or The alkoxyl of 1 to 4 carbon atom of person, particularly methoxyl group or ethyoxyl.

Here, alkylene glycol can be have 1 to 20 carbon atom, 1 to 16 carbon atom, 1 to 12 carbon atom or 1 to The alkylene glycol of 4 carbon atoms, such as, ethylene glycol or propylene glycol, and aryloxy group can be have 6 to 24 carbon atoms or The aryloxy group of 6 to 12 carbon atoms, such as phenoxy group.

Polymer can further comprise as dialkyl group (methyl) acrylamide of the monomer with nitrogen-atoms.List due to formula 1 Body is contained in polymer together with dialkyl group (methyl) acrylamide, can show the physical property of the basic demand of excellence, Including storage period, pressure-sensitive adhesion character etc., it can be ensured that suitable anti-static function and not protecting in the stripping of contact adhesive Stay residue.Such as, when only using the monomer of formula 1, the monomer of excess in a certain degree of antistatic behaviour or prevents residual side Face is effective, but is the most disadvantageous in terms of the storage period of contact adhesive.It addition, dialkyl group (methyl) ought only be used Acrylamide and when suitably controlling its proportioning, it is effective in a certain degree of antistatic behaviour or in terms of preventing residual, but Contact adhesive has abnormal flavour and cannot guarantee the balance between low speed and high speed peel strength.Therefore, by with suitable proportioning The monomer of use formula 1 and dialkyl group (methyl) acrylamide, it is possible to provide possess the contact adhesive of all above-mentioned character.

Such as, in order to meet physical property, polymer can comprise the polymerized unit of formula 1 monomer of 0.1 to 6 weight portion, with And 1 to 15 polymerized unit of dialkyl group (methyl) acrylamide of weight portion.Unless otherwise specifically limited, list used herein Position " weight portion " can refer to the weight proportion between component.Such as, state " formula 1 monomer that polymer comprises 0.1 to 6 weight portion Polymerized unit, and the polymerized unit of dialkyl group (methyl) acrylamide of 1 to 15 weight portion " mean: polymer is by comprising The monomer mixture of formula 1 monomer of weight (A) and dialkyl group (methyl) acrylamide of weight (B) with ratio (A:B) be 0.1 to 6:1 to 15 is formed.In another embodiment, polymer can comprise the polymerization of formula 1 monomer of 0.5 to 6 or 1 to 6 weight portion Unit, and the polymerized unit of dialkyl group (methyl) acrylamide of 1 to 13 or 2 to 13 weight portions may be included in described polymer In.

In the polymer, weight proportion (A) and the weight of dialkyl group (methyl) acrylamide of formula 1 monomer can additionally be controlled Proportioning (B), and weight ratio (B/A) can be controlled in such as following scope: about 0.1 to 10,0.1 to 9,0.1 to 8,0.1 to 7 Or 0.1 to 6.

Polymer can also comprise the polymerized unit of (methyl) acrylate monomer, such as (methyl) alkyl acrylate.

As (methyl) alkyl acrylate, such as in view of the cohesive strength of contact adhesive, glass transition temperature Or pressure-sensitive-adhesive, it is possible to use wherein alkyl has (methyl) alkyl acrylate of 1 to 14 carbon atom.This monomer can For: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) amyl acrylate, (first Base) 2-EHA, (methyl) acrylic acid 2-ethyl butyl ester, (methyl) n-octyl, (methyl) acrylic acid is different Monooctyl ester, (methyl) acrylic acid different nonyl ester, (methyl) lauryl acrylate or (methyl) acrylic acid myristyl ester, one therein Or at least two can be contained in polymer as polymerized unit.

Polymer can comprise the polymerized unit of (methyl) acrylate monomer of 65 to 99 weight portions, and 0.1 to 30 weight Formula 1 monomer of amount part and the polymerized unit of dialkyl group (methyl) acrylamide.In another embodiment, polymer can comprise The polymerized unit of (methyl) acrylate monomer of 70 to 90 weight portions, and formula 1 monomer of 5 to 20 weight portions and dialkyl group The polymerized unit of (methyl) acrylamide.In such scope, contact adhesive can show suitable pressure sensitive quality, and Can suitably show required physical property, such as antistatic behaviour and peel strength.

Polymer can also comprise the polymerized unit of the monomer with hydroxyl.Described polymerized unit can be that polymer provides hydroxyl Base.

As having the monomer of hydroxyl, such as, can use the monomer represented by formula 2.

[formula 2]

In formula 2, Q is hydrogen or alkyl, A and B is each independently alkylidene, and n is Arbitrary Digit, such as, and the number of 0 to 10.

In formula 2, when there is at least two [-O-B-] unit, the carbon number of the B in unit can identical or Different.

In formula 2, A and B can be each independently such as, straight-chain alkyl-sub-.

The compound of formula 2 can be but be not limited to: (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (first Base) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid 6-Hydroxyhexyl, (methyl) acrylic acid 8-hydroxy octyl ester, (methyl) Acrylic acid 2-hydroxyl glycol ester or (methyl) acrylic acid 2-hydroxyl propylene glycol ester.

Polymer can comprise, such as, and the polymerized unit and 0.5 to 30 of (methyl) acrylate monomer of 65 to 99 weight portions The polymerized unit of the monomer with hydroxyl of weight portion, or (methyl) acrylate monomer of 70 to 90 weight portions and 0.5 to The monomer with hydroxyl of 20 weight portions.In another embodiment, the monomer with hydroxyl of 1 to 15 weight portion can be comprised Polymerized unit.Within the above range, contact adhesive can show suitable cohesive strength, and is prone to guarantee desired property Can, such as antistatic property.

In one embodiment, the monomer with hydroxyl can be the two class lists existing on side chain and having different carbon number Body.

Such as, polymer can comprise polymerized unit (the wherein alkylidene present in A and B of the first monomer represented by formula 2 There is 1 to 3 carbon atom) and the polymerized unit of second comonomer that represented by formula 2 (wherein present in A and B, alkylidene has 4 to 20,4 to 16,4 to 12,4 to 8 or 4 to 6 carbon atoms).

In order to distinguish the first monomer and second comonomer, only consider by straight chain shape formed alkylidene in carbon number by terms of Count in stating carbon number, such as, when carbon containing substituent group is substituted on A and B, do not consider the carbon number of this substituent group.So, Can be provided by the polymerized unit of two kinds of hydroxyl monomers and there is the peel strength of excellence (i.e. excellent high speed and low speed are peeled off strong Balance between degree) contact adhesive.

When polymer comprises the polymerized unit of the polymerized unit of the first monomer and second comonomer, the proportioning of each monomer does not has There is an especially restriction, but polymer can comprise the of the polymerized unit of the first monomer of 0.1 to 30 weight portion and 0.1 to 10 weight portion The polymerized unit of two monomers.In another embodiment, polymer can include about 1 to 25 weight portion, 1 to 20 weight portion or 1 Polymerized unit and the of about 0.1 to 8 weight portion, 0.1 to 5 weight portion or 1 to 3 weight portion to the first monomer of 15 weight portions The polymerized unit of two monomers.In such scope, the amount that the first monomer can be bigger than second comonomer comprises in the polymer, Such as, the first monomer weight (A) can be about 1 to 25 with the ratio (A/B) of second comonomer weight (B).Another of ratio (A/B) Lower limit can be, e.g., from about 1.1 to 1.2, and another upper limit of ratio (A/B) can be, e.g., from about 20,15,10 or 8.At this In the range of sample, it is possible to provide show suitable antistatic property, will not leave behind when peeling off pollutant and show at a high speed and The contact adhesive of the appropriate balance between low-rate release strength.

When needed, polymer can also comprise known monomers prepared by the polymer for contact adhesive, such as, comprise The monomer of carboxyl, such as: (methyl) acrylic acid, 2-(methyl) acryloxyacetic acid, 3-(methyl) acryloxy propionic, 4- (methyl) acryloxy butanoic acid, acrylic acid dimer, itaconic acid, maleic acid and maleic anhydride；There is NCO Monomer；There is the monomer of glycidyl, such as (methyl) glycidyl acrylate；The free radical polymerizable list of nitrogen atom Body, such as (methyl) acrylamide, NVP or N-caprolactam；Or free radical polymerization monomer, Such as styrene.Such monomer polymerizable also comprises in the polymer, it is possible to e.g., from about 20 weight portions or lower Content is contained in described polymer.

Polymer can be by selecting the monomer of necessity from above-mentioned monomer, and by selected monomer with the mixing of desired proportion Thing is administered to polymerization such as polymerisation in solution, photopolymerization, polymerisation in bulk, suspension polymerisation or emulsion polymerization to be prepared.

Contact adhesive composition can comprise light stabilizer, such as hindered amine compound.Even if due to this light stabilizer When contact adhesive is kept at high temperature the most cohesion, so it is not result in interior clustering antistatic hereinafter described The phenomenon that the concentration of agent increases, prevents by the ether bond portions via the alkylidene oxide chain included in the polymer heated Decompose and produce free radical, or prevent the condensation with the monomer of hydroxyl, and contact adhesive composition can be significantly improved Storage stability.

Light stabilizer can be the compound such as represented by formula 3.

[formula 3]

In formula 3, M₁To M₅It is each independently R¹N、(R²)(R³)-C or (R⁴)(R⁵)-C, wherein R¹For hydrogen atom, alkyl Or alkoxyl, R²And R³It is each independently alkyl, R⁴And R⁵Being each independently hydrogen atom or alkyl, L is alkylidene or alkylene Base, and P is alkyl or the substituent group of formula 4.In formula 3, M₂To M₄In at least one is R¹-N, and with for R¹The M of-N₂、M₃Or M₄The M of next-door neighbour₁、M₂、M₃、M₄Or M₅Can be (R2) (R³)-C。

[formula 4]

In formula 4, M₆To M₁₀It is each independently R¹-N、(R²)(R³)-C or (R⁴)(R⁵)-C, wherein R¹It is hydrogen atom, alkane Base or alkoxyl, R²And R³It is each independently alkyl, and R⁴And R⁵It is each independently hydrogen atom or alkyl.In formula 4, M₇ To M₉In at least one is R¹-N, and with for R¹The M of-N₇、M₈, or M₉The M of next-door neighbour₆、M₇、M₈、M₉Or M₁₀Can be (R²)(R³)-C。

In formula 3 and 4, express " M₁To M₁₀It is R¹-N、(R²)(R³)-C or (R⁴)(R⁵)-C " mean nitrogen (N) atom or carbon (C) atom is present in M₁To M₁₀Position, and selected from R¹To R⁵Substituent group be connected with nitrogen-atoms or carbon atom.

In formula 4, labellingMean the oxygen atoms bond of the carbon atom of the formula 4 and formula 3 being connected on labelling.

In formula 3, alkylidene or alkylene base (that is, L) can be as needed for that be substituted or unsubstituted.Such as, L can be through Aryl replaces, and as aryl, can use 3, double (1,1-the dimethyl ethyl)-4-hydroxy phenyl of 5-, but the invention is not restricted to this.

In formula 3, R¹Can be such as hydrogen atom, there is 1 to 8 carbon atom or the alkyl of 1 to 4 carbon atom or have 4 To 16 or the alkoxyl of 4 to 12 carbon atoms.Alkyl or alkoxyl can be straight chains or branched, and can be by least one Individual substituent group is replaced.

In formula 3, R²、R³The alkyl with 1 to 12,1 to 8 or 1 to 4 carbon atom can be each independently with P. Alkyl can be straight chain or branched, and can be replaced by least one substituent group.

It addition, in formula 3, R⁴And R⁵It can be hydrogen atom.

It addition, in formula 3, L can be the alkylidene such as with 4 to 12 or 6 to 10 carbon atoms, or have 2 to 10 or the alkylene base of 4 to 8 carbon atoms.Alkylidene or alkylene base can be straight chains or branched, and can be by least one Individual substituent group is replaced.

The compound of formula 3, can be but be not limited to: the most double (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1, 2,2,6,6-pentamethyl-4-piperidyl decanedioic acid methyl ester, 2-[[3,5-double (1,1-dimethyl ethyl)-4-hydroxy phenyls] first Base]-2-butyl-1,3-malonic acid double (1,2,2,6,6-pentamethyl-4-piperidyl) ester, double (2,2,6,6-tetramethyl-4-piperidines Base) sebacate or double-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyls) sebacate, but the present invention is not restricted to This.

Relative to the polymer of 100 weight portions, the light stabilizer that can comprise in contact adhesive composition be 0.01 to 10 weight portions, 0.05 to 10 weight portion, 0.05 to 8 weight portion, 0.05 to 6 weight portion or 0.05 to 5 weight portion.Join such Under Bi, it is possible to provide such contact adhesive composition: its can be effectively prevented by the decomposition of alkylidene oxide chain be produced from by The condensation of the monomer of base or hydroxyl, and there is the storage stability of excellence.

Contact adhesive composition can also comprise cross-linking agent, and it is reacted to form cross-linked structure with the crosslinking points of polymer.

It is, for example possible to use aliphatic isocyanate cross-linking agent is as described cross-linking agent.When cross-linking agent (i.e. wraps with polymer There is the polymer of the monomer of hydroxyl containing at least two) when forming cross-linked structure, can obtain having suitable low speed and at a high speed The contact adhesive of the antistatic property of peel strength and necessity.

It is, for example possible to use comprise aliphatic cyclic isocyanate compound and/or aliphatic non-annularity isocyanation esterification The cross-linking agent of compound is as described cross-linking agent.Term " aliphatic cyclic isocyanate compound " can refer to comprise do not correspond to herein The isocyanate compound of the circulus of aromatic ring, and term " aliphatic non-annularity isocyanate compound " can refer to example As, acyclic straight or branched isocyanate compound.Here, aliphatic cyclic isocyanate compound can be, such as Isocyanate compound, such as isophorone diisocyanate, methylene biscyclohexyl diisocyanate or hexamethylene two isocyanide Acid esters, in its derivant such as its dimer or trimer, or aforesaid compound, any one and polyhydric alcohol are (such as trihydroxy methyl third Alkane) product；And " aliphatic non-annularity isocyanate compound " can be C1 to C20, C1 to C16, C1 to C12 or C1 To 8C alkylene diisocyanate compound, such as hexamethylene diisocyanate, its derivant such as its dimer or trimer, or Any one in person's aforesaid compound and the product of polyhydric alcohol (such as trimethylolpropane)；But the application is not limited to this.

Herein, when being used together aliphatic cyclic isocyanate compound and aliphatic non-annularity isocyanate compound Time, their ratio is not particularly limited, and can carry out suitable selection as required.Generally, relative to the fat of 100 weight portions The ring-type isocyanate compound of fat race, the aliphatic that cross-linking agent can include about 1 to 500 weight portion or 20 to 300 weight portions is non- Ring-type isocyanate compound.Can use commercially available MHG-80B and the Duranate P such as produced by Asahi and by The NZ-l that BAYER produces, as cross-linking agent, i.e. comprises aliphatic cyclic isocyanate compound and aliphatic non-annularity Carbimide. The cross-linking agent of ester compounds.

When requiring otherwise, it be also possible to use following known cross-linking agent, such as: epoxy crosslinking agent, as ethylene glycol bisthioglycolate shrinks Glycerin ether, triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, N, N, N ', N '-four glycidyl group ethylenediamine or sweet Oil diglycidyl ether；Aziridine crosslinker, such as N, N '-Toluene-2,4-diisocyanate, 4-bis-(1-aziridine Methanamide), N, N '-diphenyl-methane- 4,4 '-two (1-aziridine Methanamides), triethylenemelanin, double isophthaloyl-1-(2-methylaziridine) (bisisoprothaloyl-1-(2-methylaziridine)) or three-1-'-aziridino phosphine oxides；Or metal chelating Compound cross-linking agent, such as by polyvalent metal such as aluminum, ferrum, zinc, stannum, titanium, antimony, magnesium and/or vanadium and acetylacetone,2,4-pentanedione or acetoacetic acid The compound of ethyl ester coordination preparation.

Relative to the polymer of 100 weight portions, contact adhesive composition can comprise 0.01 to 10 weight portion or 0.01 Cross-linking agent to 5 weight portions.Within the above range, available suitable cross-linked structure and can be by the low speed of contact adhesive and height Speed peel strength controls in expected range.

Contact adhesive composition can also comprise antistatic additive.It is, for example possible to use ionic compound is as antistatic Agent, and as anion, can use and comprise two (fluorosulfonyl) imido ionic compound.Described two (fluorosulfonyl) acyl Imines can have electricity stable form, thus stably provide antistatic property for contact adhesive.

The anion-containing various compounds of bag (such as inorganic salt or organic salt) can be used as ionic compound.As nothing Machine salt, such as, can use and comprise anion and the change of metal cation (such as alkali metal cation or alkaline earth metal cation) Compound.Considering ion stability and mobility, cation can be: lithium ion (Li⁺), sodium ion (Na⁺), potassium ion (K⁺), rubidium from Son (Rb⁺), cesium ion (Cs⁺), beryllium ion (Be²⁺), magnesium ion (Mg²⁺), calcium ion (Ca²⁺), strontium ion (Sr²⁺) and barium ions (Ba²⁺In one in) or at least two, preferably lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion and barium ions One or at least two, and more preferably lithium ion.

When ionic compound is organic salt, the organic salt comprising cation and anionic group can be used, described sun from Son is such as: quaternary ammonium compound, such as N-ethyl-N, N-dimethyl-N-propyl ammonium, N, N, N-trimethyl-N-propyl ammonium, N-methyl- N, N, N-tributyl ammonium, N-ethyl-N, N, N-tributyl ammonium, N-methyl-N, N, N-tri-hexyl ammonium, N-ethyl-N, N, N-tri-oneself Base ammonium, N-methyl-N, N, N-trioctylammonium or N-ethyl-N, N, N-trioctylammonium；, such as tetraalkylOr it derives Thing；PyridineOr derivatives thereof, tetrahydropyridineOr derivatives thereof, dihydropyridineOr derivatives thereof, imidazolesOr it derives Thing, the compound or derivatives thereof comprising pyrrolin skeleton, the compound or derivatives thereof comprising pyrrole skeleton, imidazoline (imidazolinium) such as 1-ethyl-3-methylimidazoleOr derivatives thereof, pyrazolesOr derivatives thereof, trialkyl sulfonium or its Derivant, pyrrolidineSuch as 1-methyl isophthalic acid-propyl pyrrole alkaneOr derivatives thereof or piperidinesSuch as 1-methyl isophthalic acid-propylpiperdineOr derivatives thereof.As organic salt, can use and above-mentioned cation comprises the sun that wherein alkyl is replaced by alkynyl or epoxy radicals The compound of ion.

Relative to the polymer of 100 weight portions, contact adhesive composition can comprise such as 0.01 to 5 weight portion, 0.1 To 5 weight portions, 0.1 to 4 weight portion, 0.1 to 3 weight portion, 0.1 to 2 weight portion or the ionic compound of 0.1 to 1 weight portion, but The application is not particularly limited to this.Consider the compatibility between desired antistatic behaviour or component, the proportioning of ionic compound can be changed.

Contact adhesive composition can also comprise silane coupler.Coupling agent can be the following a kind of or mixing of at least two Thing: γ-glycidoxypropyl group triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy Hydroxypropyl methyl diethoxy silane, γ-glycidoxypropyl group triethoxysilane, 3-mercaptopropyi trimethoxy silane, second Thiazolinyl trimethoxy silane, VTES, γ-methacryloxypropyl trimethoxy silane, γ-methyl Acryloxypropyl triethoxysilane, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, 3- Isocyanate group triethoxysilane, γ-acetoacetyl propyl trimethoxy silicane, γ-acetoacetyl propyl triethoxy Silane, beta-cyano acetyl group trimethoxy silane, beta-cyano acetyl group triethoxysilane and acetoxyl group acetyl trimethoxy Silane.Such as, as silane coupler, it is preferably used and there is acetoacetate groups or the silane coupler of beta-cyano acetyl group. Relative to the polymer of 100 weight portions, contact adhesive composition can comprise 0.01 to 5 weight portion or 0.01 to 1 weight portion Silane coupler.Within the above range, suitable pressure-sensitive adhesion intensity can be improved and guarantee durability and reliability.

Contact adhesive composition can also comprise viscosifier to control pressure-sensitive adhesion performance.Viscosifier can be: based on hydrocarbon Resin or its hydrogenated products, rosin resin or their hydrogenated products, rosin ester resin or their hydrogenated products, terpene resin Or their hydrogenated products, terpene phenol resin or their hydrogenated products, polymeric rosin resin or polymeric rosin ester resin, it can It is used alone or at least two is applied in combination.Relative to the polymer of 100 weight portions, compositions can comprise 1 to 100 weight portion Viscosifier.When above-mentioned content range, it can be ensured that the suitable Overlay of the compatibility and enhancing, and cohesive strength.

Contact adhesive composition can comprise at least one selected from following additive: can form coordinate bond with antistatic additive Coordination compound, light trigger, polyfunctional acrylic ester, epoxy resin, cross-linking agent, UV stabilizer, antioxidant, coloring Agent, reinforcing agent, filler, foaming agent, surfactant and plasticizer, as long as it does not affect desired effects.

When realizing cross-linked structure, contact adhesive composition is to the bur that surface can be 30mN/m or lower Low-rate release strength can be about 1 to 40gf/25mm, 1 to 30gf/25mm, 1 to 20gf/25mm or 1 to 10gf/25mm；High Speed peel strength be about 10 to 300gf/25mm, 10 to 250gf/25mm, 10 to 200gf/25mm, 10 to 150gf/25mm or 10 to 100gf/25mm.

The terms " low-rate release strength " can be, such as, in the peel angle of 180 degree and the stripping of 0.3m/ minute The peel strength recorded under speed；" high speed peel strength " can be the detachment rate of the peel angle in 180 degree and 30m/ minute The peel strength of lower mensuration.

Especially, the contact adhesive composition the most realizing cross-linked structure can sticked to surface by each peel strength After being on the bur of 30mN/m or lower and keeping 24 hours at the temperature of 23 DEG C and the relative humidity of 65%, Yu Qian State and record under peel angle and detachment rate.The concrete grammar measuring peel strength will illustrate in embodiments below.

The surface of bur can assay method can be known mensuration surface can method, but the application limits the most especially and This.For example, it is possible to by the contact angle gauging surface energy measuring bur, or known surface can be used to survey by determinator Determine surface energy.The surface of bur can be e.g., from about 10 to 30mN/m.

The high speed peel strength (H) of contact adhesive composition and the ratio (H/L) of low-rate release strength (L) can be 1 to 30,1 to 25,1 to 20,1 to 15,5 to 15 or 7 to 13.

Realizing under cross-linked structure state wherein, contact adhesive composition can have the stripping of 0.5kV or lower Static discharge (ESD), described static discharge is can be with the peel angle of 180 degree the bur for 30mN/m or lower from surface Produce when detachment rate with 40m/ minute is peeled off.The assay method peeling off ESD will describe in embodiments below.

When guaranteeing above-mentioned low speed and high speed peel strength and/or peeling off ESD, it is right that contact adhesive composition can show The suitable defencive function of bur, can make electrostatic minimize, it is possible to peeled off easily at a high speed.

On the other hand, the application provides pressure-sensitive adhesive sheet.Pressure-sensitive adhesive sheet can be, such as, protecting film, particularly use Protecting film in optics.

Such as, pressure-sensitive adhesive sheet can serve as the protecting film of following optics, such as Polarizer, the polarizer, is polarized Device protecting film, compensation film for angular field of view and brightness enhancement film.Term used herein " polarizer " and " Polarizer " are different Object.It is to say, the polarizer refers to show the film of polarization function, sheet or device, and Polarizer refers to except the polarizer The optics of other assembly in addition.As other element that may be included in addition to the polarizer in optics, can use Device protecting film or phase shift films partially, but the application is not limited to this.

Pressure-sensitive adhesive sheet can comprise, such as, for protecting the basement membrane on surface and on a surface of this basement membrane Pressure sensitive adhesive layer.Pressure sensitive adhesive layer can comprise, such as, the contact adhesive composition of crosslinking, wherein realize crosslinking The contact adhesive composition of structure, as described contact adhesive composition.

After realizing cross-linked structure, contact adhesive composition shows relatively high low-rate release strength and relatively low High speed peel strength, excellent balance between two kinds of peel strengths, excellent durability and reliability, operability, transparent Degree and antistatic behaviour.Therefore, protecting film can effectively serve as surface protection film with protect various optics or parts or Display device or parts, such as the surface of following optics: in such as LCD, the Polarizer of use, retardation plate, optics are mended Repay thin film, reflector plate and brightness enhancing films, but such use is not limited to protecting film.

General purpose film known in the art and sheet may serve as the basement membrane of surface protection.Such as, for surface protection Basement membrane can be plastic foil, the polyester such as formed by polyethylene terephthalate or polybutylene terephthalate (PBT) Film, poly tetrafluoroethylene, polyethylene film, polypropylene screen, polybutene film, polybutadiene film, poly-(vinyl chloride) film or polyimides Film.This film can be made up of or be the packed structures of at least two-layer monolayer, and in some cases, can farther include function Layer, such as anti-pollution layer or antistatic layer.It addition, in order to strengthen basement membrane cohesiveness, the one or both sides of basement membrane can be entered Row surface processes, such as prime treatment.

The thickness of basement membrane is not particularly limited, and suitably can select according to purposes, and usually 5 to 500 μm or Person 10 to 100 μm.

The thickness of the pressure sensitive adhesive layer being contained in pressure-sensitive adhesive sheet is not particularly limited, and can be e.g., from about 2 to 100 μm or 5 to 50 μm.

The method forming pressure sensitive adhesive layer is not particularly limited, such as, can be: use usual manner (such as bar coater) Coating on base films contact adhesive composition or the coating solution prepared by said composition of coating solidification have been coated with pressure-sensitive Adhesive composition, or on the surface of peelable base material, coat contact adhesive composition or coating solution, solidified The contact adhesive composition of coating or coating solution, afterwards by the contact adhesive composition having been coated with or coating solution It is transferred to basement membrane.

The technique forming pressure sensitive adhesive layer can fully remove in contact adhesive composition or coating solution Carry out after volatile component or bubbling component such as reaction residue.Accordingly it is possible to prevent too low due to contact adhesive Crosslink density or molecular weight and problem that the elastic modelling quantity that causes reduces, and owing to being at high temperature present in glass plate and pressure Increased air bubble between sensitive adhesive layer and the problem that forms scattering in described pressure sensitive adhesive layer.

In above-mentioned technique, the method for cured pressure-sensitive adhesive agent compositions is it is not also specifically limited, can be by suitable ripe Metallization processes (cross-linking agent and the polymer reaction being contained in compositions can be made) or use light radiation (such as ultraviolet radiation, It can cause the activation of wherein light trigger) carry out.

Pressure sensitive adhesive layer can have, the gel content of e.g., from about 80% to 99%.Gel content can be by such as table Reach formula 1 to calculate.

[expression formula 1]

Gel content=B/A × 100

In expression formula 1, A is the quality of contact adhesive, and B is at room temperature to be soaked in ethyl acetate by contact adhesive The dry mass of the insoluble content that stain was reclaimed after 48 hours.

In yet another aspect, the application provides optics.Exemplary optics device can include optical element and adhere to The contact adhesive of described optical element surface.Such as, the pressure sensitive adhesive layer of pressure-sensitive adhesive sheet adheres to optical element Surface, and thus can be by for protecting the basement membrane on surface to protect optical element.

The optical element being contained in optics can be, the such as polarizer, Polarizer, polarizer protective film, retardation layer Or viewing angle compensating layers.

Here, as the polarizer, it is possible to use general type known in the art, the such as polyvinyl alcohol polarizer.

The polarizer is functional membrane or sheet, and it only extracts from the incident illumination vibrated with multiple directions and shakes in one direction Dynamic light.This polarizer can be, such as, and the shape that dichroic dyestuff is absorbed and is orientated on resin molding based on polyvinyl alcohol Formula.The resin based on polyvinyl alcohol constituting the polarizer can be obtained by such as gelatine resin based on polyvinyl acetate ?.In this case, in addition to the homopolymer of vinyl acetate, in spendable resin based on polyvinyl acetate Comprise the steps that vinyl acetate and the polymer of the different monomers copolymerizable with vinyl acetate.Here, can with vinyl acetate altogether The example of poly-monomer can be but be not limited to: unsaturated carboxylic acid, alkene, vinyl ethers, unsaturated sulfonic acid and have the third of ammonium The mixture of a kind of or at least two in acrylamide.The degree of gelation of resin based on polyvinyl alcohol can be about 85 to 100mol%, preferably 98mol% or higher.Resin based on polyvinyl alcohol such as can also be it be also possible to use by the most modified The polyvinyl formal modified with aldehyde or polyvinyl acetal.Additionally, the degree of polymerization of resin based on polyvinyl alcohol is About 1000 to 10000, preferably from about 1500 to 5000.

Use resin based on polyvinyl alcohol can form the disc-shaped membrane of the polarizer.Use resin formation based on polyvinyl alcohol The method of film is not particularly limited, and can be known in the art conventional method.The disc-shaped membrane of resin formation based on polyvinyl alcohol Thickness be not particularly limited, such as, can be appropriately controlled in 1 to 150 μ m.In view of stretching feasibility, disc-shaped membrane Thickness be controllable to 10 μm or higher.The polarizer can be prepared by following technique: stretching (such as uniaxial tension) is based on poly-second The technique of the resin molding of enol, uses dichroic dyestuff to dye resin molding based on polyvinyl alcohol and absorbs dichroic dye The technique of material, the technique processing the resin molding based on polyvinyl alcohol absorbing dichroic dyestuff with boric acid aqueous solution, Yi Ji The technique washing resin molding based on polyvinyl alcohol with boric acid aqueous solution after processing.Here, as above-mentioned dichroic dyestuff, can To use iodine or dichroic organic dyestuff.

Polarizer can include the such as polarizer；Another blooming with the one side or two sides adhering to the polarizer.Here, Above-mentioned polarizer protective film, retardation layer, viewing angle compensating layers or antiglare layer can be used as another blooming.

Herein, polarizer protective film can be the protecting film for the polarizer, itself and the protection including pressure sensitive adhesive layer Film is different.As polarizer protective film, such as, can use and pile up by the multilayer film of the following protecting film constituted: based on fiber The film such as tri acetyl cellulose of element；Acryloyl basement membrane (acryl film)；Film based on polyester such as polycarbonate membrane or poly-right PET film；Film based on polyether sulfone；And/or based on polyolefinic film such as polyethylene film, polypropylene screen, have Ring-type or the polyolefin film of norborene structure or ethylene propylene polymerization thing.The thickness of protecting film it is not also specifically limited, because of As long as this can form common thickness.

Surface-treated layer can be there is by protecting film on the surface of the optical element protected in optics.Surface Reason layer can have, the surface energy of such as 30mN/m or lower.It is to say, in optics, can protected by protecting film Optical element surface on to form surface can be the surface-treated layer of 30m N/m or lower, and the contact adhesive of protecting film Layer can adhere to surface-treated layer.

Surface-treated layer can be high rigidity layer, the most anti-dazzle (AG) layer of antiglare layer or half dizzy (SG) layer, or low reflection layer is as anti- Reflection (AR) layer or low reflection (LR) layer.

High rigidity layer can be the layer under 500 grams of load with at least 1H or 2H pencil hardness.Pencil hardness can be such as Use and measure according to the pencil-lead of regulation in the KS G2603 in ASTM D3363 standard.

High rigidity layer can be such as high hardness resin layer.Resin bed can include such as cure states room-temperature-curable, wet can Solidification, heat solidifiable or the resin combination of active energy ray-curable.In one embodiment, resin bed includes solid Change heat solidifiable or the resin combination of active energy ray-curable of state, or the active energy ray-curable of cure states Resin combination.In high rigidity layer illustrates, " cure states " refers to such state: wherein comprise in every kind of resin combination Component stand cross-linking reaction or polyreaction, thus resin combination is changed into hard state.It addition, room temperature can herein Solidification, the resin combination of wet curable, heat solidifiable or active energy ray-curable can be at room temperature solidify or By applying heat or by the compositions of active energy beam radiation curing under the suitable humidity of person.

The various resin combinations of the pencil hardness meeting above-mentioned scope in cure states are to it known in the art, and this area Those of ordinary skill can be readily selected suitable resin combination.

In one embodiment, resin combination can include acryl compound, epoxide, urethane chemical combination Thing, phenolic compounds or petchem are as its key component." compound " can be monomer, oligomeric or polymerization chemical combination Thing.

In one embodiment, resin combination can be to have excellent optical properties such as transparency and excellent resistant to yellowing Acryl compositions, the acryl compositions of such as active energy ray-curable.

The acrylic composition of active energy ray-curable can include, such as, active energy beam is polymerisable poly- Polymer component and the monomer for reactivity dilution.

Polymers compositions can be the component known in the art as active energy beam polymerizable oligomers, such as urethane third Olefin(e) acid ester, epoxy acrylate, ether acrylate and ester acrylate, or comprise monomer such as (methyl) acrylate monomer The polymer of mixture.Here, (methyl) acrylate monomer can be (methyl) alkyl acrylate, have (methyl) of aryl Acrylate, heterocycle (methyl) acrylate or alkoxyl (methyl) acrylate.Prepare the group of active energy ray-curable The various polymers compositionss of compound are to it known in the art, and can select above-claimed cpd as required.

As the monomer for reactivity dilution in the acryloyl compositions that may be included in active energy ray-curable Can be that there is functional group (the such as acryloyl group or metering system of or at least two active energy ray-curable Acyl group) monomer.Such as (methyl) acrylate monomer or polyfunctional acrylic ester can be used as reactivity dilution Monomer.

Prepare selection and the mixed proportion of selected component of the component of the acryloyl compositions of active energy ray-curable It is not particularly limited, and can control according to the hardness of expectation resin bed and other physical property.

As antiglare layer, the most described AG layer or SG layer, can use such as have uneven surface resin bed or Person comprises the resin bed with the granule with resin bed refractive index different refractivity.

Herein, above-mentioned resin bed can use such as forming the resin bed of high rigidity layer.When forming antiglare layer, no The component of the resin combination for resin bed must be controlled to possess high rigidity, but the resin bed showing high rigidity can be formed.

Herein, the method forming uneven surface on the resin layer is not particularly limited.Such as, resin combination is worked as Coating with can make resin composition when there is the contacting dies expecting uneven structure, or suitable by making to have The granule of particle diameter mixes with resin combination, coats and solidifies mixture and can realize uneven structure.

Antiglare layer can also use to be had refractive index and is different from the granule of resin bed refractive index and realizes.

In one embodiment, the difference of the refractive index between granule and resin bed can be 0.03 or lower, or 0.02 To 0.2.If the difference of refractive index is too small, then it is difficult to produce mist degree；If refractive index difference is excessive, then resin bed produce big Amount scattering, thus increase mist degree, but the reduction of light transmittance or contrast performance can be caused.Consider that these factors are optional suitably Granule.

The shape of the granule included in resin bed is not particularly limited, and can be such as, spherical, elliposoidal, polyhedron shape, Amorphous or other shape.The mean diameter of granule is 50 to 5000nm.In one embodiment, can use have concavo-convex The granule on uneven surface is as granule.The average surface roughness (Rz) of this granule can be, such as 10 to 50nm or 20 to 40nm, And/or protruding maximum height can be about the width between 100 to 500nm or 200 to 400nm and projection on uneven surface Can be about 400 to 1200nm or 600 to 1000nm.This granule has the compatibility with resin bed of excellence or can resin Dispersibility in Ceng.

As granule, various inorganic or organic granular can be used.Inorganic particle can be: Silicon stone, amorphous titania, Amorphous zirconium, Indium sesquioxide., aluminium oxide, amorphous zinc oxide, amorphous cerium, Barium monoxide, calcium carbonate, amorphous metatitanic acid Barium or barium sulfate；Organic granular can be to comprise organic material such as acryl, styrene resin, urethane resin, melamine The cross-linking products of polyimide resin, benzoguano amine resin, epoxy resin or silicone resin or the granule of non-crosslinked product, but the application is not It is limited to this.

The uneven structure formed on resin bed and the content of granule are not particularly limited.Uneven structure can be controlled Shape or the content of granule, be used in the mist degree of the resin bed of AG layer be about 5% to 15%, 7% to 13% or 10%, or the mist degree being used in the resin bed of SG layer is about 1% to 3%.Mist degree can use mist according to the handbook of manufacturer Degree meter such as measures purchased from HR-100 or HM-150 of Sepung.

Low reflection layer such as AR layer or LR layer can be formed by coating low reflective material.The each of low reflection layer can be formed It is known for planting low reflective material, and can properly select and for optics.Can be by coating low reflective material shape Become low reflection layer with the reflectance with about 1% or lower.

Can also use Korean unexamined patent publication no No.2007-0101001,2011-0095464,2011-0095004, 2011-0095820、2000-0019116、2000-0009647、2000-0018983、2003-0068335、2002- 0066505、2002-0008267、2001-0111362、2004-0083916、2004-0085484、2008-0005722、 Material disclosed in 2008-0063107,2008-0101801 or 2009-0049557 is to form surface-treated layer.

Single surface-treated layer, or the surface-treated layer of the combination with at least two can be formed.Described combination can be led to Cross formation high rigidity layer on the surface of basic unit, be formed on low reflection layer the most again and formed.

It yet still another aspect, the application provides display device, such as liquid crystal display (LCD).Exemplary display device can be wrapped Include liquid crystal panel and optics adheres on one or two faces of liquid crystal panel.Film can use such as binding agent or Person's contact adhesive adheres to liquid crystal panel.Here, described binding agent or contact adhesive with in said protection film Binding agent that contact adhesive is different or contact adhesive.

The type of the liquid crystal panel comprised in LCD is not particularly limited.Such as, the type of liquid crystal panel does not limit, can Use all types of known liquid crystal panel, including: all types of passive matrix panels, including twisted nematic (TN) type, surpass Twisted nematic (STN) type, ferroelectricity (F) type and polymer dispersion LCD (PD LCD)；All types of active matrix panels, bag Include both-end subtype and three terminal type panels；Coplane conversion type (IPS) panel；With vertical orientated (VA) profile plate.Additionally, for Type and the manufacture method thereof of other assembly comprised in LCD are it is not also specifically limited, the general components of this area can be used And it is unrestricted.

Beneficial effect

The contact adhesive composition of the application can show the storage stability of excellence, closes after forming cross-linked structure Suitable low speed and high speed peel strength and marginal excellent balance.Therefore, use when contact adhesive composition The protected effect of excellence can be shown when protecting film, can be peeled off easily when peeling off at a high speed, and be thus advantageous to add at a high speed Work, and the anti-static function of excellence can be shown.

Detailed description of the invention

Hereinafter, describe reference example and comparative example in detail contact adhesive composition, but contact adhesive combines The scope of thing is not limited to following example.

Physical property in embodiments herein and comparative example is estimated in the following manner.

1. the mensuration of storage period

Within 0 hour and 24 hours, measure by cross-linking agent is each with prepared by the polymer mixed prepared in advance after the production The viscosity of the coating solution (contact adhesive composition) of embodiment or comparative example, afterwards according to following criterion evaluation storage period. Here, viscosity is measured by the following method: utilize Brookfield viscometer (DV-II+) that coating solution is put into 250mL glass To have the weight of about 200g in Ping, and keep this bottle in being maintained at the constant temperature bath of 23 DEG C 30 minutes putting down reaching temperature Weighing apparatus, measures viscosity in the RPM interval of the torque keeping confidence interval.

O: after preparing 24 hours (from the beginning of 0 hour), viscosity B coefficent is less than 30%

X: after preparing 24 hours (from the beginning of 0 hour), viscosity B coefficent is 30% or higher

2. the mensuration of low-rate release strength

According to JIS Z 0237, the roller of 2kg is used to be adhered to by the pressure-sensitive adhesive sheet of preparation in embodiment or comparative example The antiglare layer being formed on Polarizer.Then, products therefrom is kept 24 hours under 23 DEG C and 65% relative humidity, then cuts Cut the size with 25mm x 120mm (wide x length), thus prepare sample.Subsequently, sample is fixed on the glass substrate, so Rear use extensiometer with the detachment rate of the peel angle of 180 degree and 0.3m/ minute in the horizontal direction by contact adhesive Sheet is peeled off from antiglare layer, to measure peel strength.Measure the peel strength of two same sample, average.

3. the mensuration of high speed peel strength

According to JIS Z 0237, the roller of 2kg is used to be adhered to by the pressure-sensitive adhesive sheet of preparation in embodiment or comparative example The antiglare layer being formed on Polarizer.Then, products therefrom is kept 24 hours under 23 DEG C and 65% relative humidity, then cuts Cut the size with 25mm x 250mm (wide x length), thus prepare sample.Subsequently, sample is fixed on the glass substrate, so Rear use extensiometer with the detachment rate of the peel angle of 180 degree and 30m/ minute in the horizontal direction by pressure-sensitive adhesive sheet Peel off from antiglare layer, to measure peel strength.Measure the peel strength of two same sample, average.

4. peel off the mensuration of static discharge (ESD)

To prepare sample with the identical method described in the mensuration of low speed and high speed peel strength, except sample has about Outside the size of 22cm x 25cm (wide x length).Afterwards, sample is fixed on the glass substrate, use extensiometer with about The pressure-sensitive adhesive sheet of sample is peeled off by the peel angle of 180 degree and the detachment rate of 40m/ minute, peels off ESD to measure.

5. remove the spot after pressure-sensitive adhesive sheet

Will the identical sample used in the pressure-sensitive adhesive sheet mensuration from low-rate release strength peel off, observe due to Electrostatic spot on sticker surface is also estimated according to following standard.

Spot is not observed on the surface of A: bur

Spot is observed on the surface of B: bur

Preparation example 1: the preparation of acrylic acid (ester) base polymer (A)

By the 2-EHA (2-EHA) of 85 weight portions, acrylic acid 4-hydroxy butyl ester (4-HBA) of 2 weight portions, 5 The polyethyleneglycol first of acrylic acid 2-hydroxyl ethyl ester (2-HEA), the DMAA of 3 weight portions and 5 weight portions of weight portion Base ether metacrylic acid ester (oxyethylene units adds molal quantity: 9mol) adds to equipped with carrying out nitrogen reflux and being prone to Control the 1L reactor of the chiller of temperature, add the ethyl acetate of 100 weight portions afterwards as solvent.Subsequently, nitrogen is used Purge 1 hour to remove oxygen, add reaction initiator (AIBN: azodiisobutyronitrile) with reaction about 8 hours, use ethyl acetate Diluting reaction product.Thus prepare acrylic acid (ester) base polymer A.

Preparation example 2 to 9: the preparation of acrylic acid (ester) base polymer B to I

Acrylic acid (ester) base polymer is prepared, except being used for preparing polymer with the method identical with described in preparation example 1 The proportioning of monomer change into as shown in table 1.

[table 1]

Embodiment 1

The preparation of contact adhesive composition

By following contact adhesive composition of preparing: birds of the same feather flock together relative to the acrylic acid (ester) of 100 weight portion preparation examples 1 Compound (A), is uniformly blended into the cross-linking agent based on isophorone diisocyanate as cross-linking agent of 5.0 weight portions and based on six The mixture (MHG-80B, Asahi chemical company (AKCC)) of the cross-linking agent of methylene diisocyanate and 0.5 weight portion Two (trifluoromethane sulfonyl group) imide li (LiTFSi), and consider that obtained mixture is diluted to suitably by paintability Concentration.

The preparation of pressure-sensitive adhesive sheet

Prepared by coating on a surface of poly-(ethylene glycol terephthalate) (PET) film (thickness: 38 μm) Contact adhesive composition and be dried, formed uniform coating to have thickness about 20 μm.Subsequently, coating is protected at about 90 DEG C Hold 3 minutes to cause cross-linking reaction, thus prepare pressure-sensitive adhesive sheet.

Embodiment 2 to 4 and comparative example 1 to 5

Contact adhesive composition is prepared, except each contact adhesive composition with the method identical with described in embodiment 1 Composition and ratio change into as shown in tables 2 and 3.

[table 2]

[table 3]

Have evaluated the physical property of the contact adhesive composition of embodiment and comparative example, result is summarised in table 4 and 5.

[table 4]

[table 5]

Claims

1. a contact adhesive composition, comprises:

Comprise the Acrylic polymer of following polymerized unit: formula 1 monomer of 0.1 to 6.0 weight portion, the two of 1 to 15 weight portion Alkyl (methyl) acrylamide, and the monomer comprising hydroxyl of 1 to 20 weight portion；And

Ionic compound；And

Cross-linking agent；

[formula 1]

Wherein Q is hydrogen or the alkyl with 1 to 4 carbon atom, and U is the alkylidene with 1 to 4 carbon atom, and Z is hydrogen, tool There is the alkyl of 1 to 4 carbon atom or there is the aryl of 6 to 20 carbon atoms, and m is the number of 1 to 12,

The wherein said monomer comprising hydroxyl includes the first monomer represented by formula 2 and 0.1 to 5 weight of 0.1 to 15 weight portion The second comonomer represented by formula 2 of amount part, in described first monomer, the alkylidene of A and B has 1 to 3 carbon atom, and described second In monomer, the alkylidene of A and B has 4 to 8 carbon atoms:

[formula 2]

Wherein Q is hydrogen or the alkyl with 1 to 4 carbon atom, A and B is alkylidene independently of one another, and n is the number of 0 to 10.

Contact adhesive composition the most according to claim 1, the weight of the first monomer described in wherein said polymer Proportioning (A) is 1 to 10 with the ratio (A/B) of the weight proportion (B) of second comonomer described in described polymer.

Contact adhesive composition the most according to claim 1, wherein said ionic compound is inorganic salt or organic salt.

Contact adhesive composition the most according to claim 1, wherein said cross-linking agent is aliphatic isocyanates crosslinking Agent.

Contact adhesive composition the most according to claim 1, wherein said cross-linking agent comprises selected from following at least one Kind: aliphatic cyclic isocyanate compound and aliphatic non-annularity isocyanate compound.

Contact adhesive composition the most according to claim 5, wherein said aliphatic cyclic isocyanate compound is Selected from isophorone diisocyanate, methylene biscyclohexyl diisocyanate and the isocyanation esterification of cyclohexane diisocyanate Compound；The dimer of described isocyanate compound or trimer；Or the reaction of described isocyanate compound and polyhydric alcohol produces Thing.

Contact adhesive composition the most according to claim 5, wherein said aliphatic non-annularity isocyanate compound For: C1-C20 alkylene diisocyanate compound；The dimer of described isocyanate compound or trimer；Or described isocyanide Ester compound and the product of polyhydric alcohol.

Contact adhesive composition the most according to claim 1, wherein relative to the described polymer of 100 weight portions, institute The content stating cross-linking agent is 0.01 to 20 weight portion.

9. a surface protection film, including:

Surface protection basal layer；And

Be formed at the pressure sensitive adhesive layer on one or two surface of described basal layer, its comprise cross-linked state according to right Require the contact adhesive composition described in 1.

Surface protection film the most according to claim 9, relative to surface can be wherein 30mN/m or lower bur with The peel strength of the pressure sensitive adhesive layer that the detachment rate of the peel angle of 180 degree and 0.3m/ minute measures be 1gf/25mm extremely 40gf/25mm。

11. surface protection films according to claim 9, relative to surface can be wherein 30mN/m or lower bur with The peel strength of the pressure sensitive adhesive layer that the detachment rate of the peel angle of 180 degree and 30m/ minute measures be 10gf/25mm extremely 150gf/25mm。

12. 1 kinds of optics, protecting film the most according to claim 9 is adhered to the to be stripped of described optics Surface.

13. optics according to claim 12, the described surface being wherein stained with described protecting film has 30mN/m Or lower surface energy.

14. 1 kinds of display devices comprising optics according to claim 12.